Photopolymerizable composition

ABSTRACT

A photopolymeric composition having improved sensitivity to a visible light ray which comprises: 
     (a) at least one ethylenic unsaturated compound which is non-gaseous at a normal temperature; 
     (b) at least one metallic arene compound; 
     (c) a compound selected from the group consisting of p-aminophenyl unsaturated detone compounds, pyridine derivatives or salts thereof, xanthene or thioxanthene compounds and mixtures thereof; and optionally 
     (d) a compound selected from the group consisting of phenylglycine derivatives, cyclic diketone compounds and mixtures thereof.

FIELD OF THE INVENTION

The present invention relates to a novel photopolymerizable compositionhaving sensitivity up to a visible light range.

BACKGROUND OF THE INVENTION

Photopolymerizable compositions have been used for various purposes. Forexample, they are used for printing, copying, resist formation and thelike, commercially.

In general, these compositions contain ethylenic unsaturated compoundsor other types of polymerizable compounds, photopolymerizationinitiators or photo-polymerization initiator systems and, preferably,solvent-soluble or water or alkali-soluble organic polymer bindercompounds. However, the application of many of these known and usefulphotopolymerizable compositions is restricted because most of theinitiators used are activated only by an ultraviolet range of aspectrum.

Further, as a technique for image formation, it is demanded that avisible light ray is used as a light source in place of an ultravioletray, or an exposure to light is carried out by scanning with a laserwhich has a large oscillation strength at a visible light range, forexample, an argon ion laser. Accordingly, a photopolymerizable materialhaving high sensitivity to a visible light ray is demanded and, thereby,a photopolymerization initiator having high sensitivity to a visiblelight ray is required.

As improved photopolymerization initiator systems, there are disclosed asystem containing hexaarylbisimidazole in Japanese Patent Kokai No. 292,corresponding to U.S. Pat. No. 4,162,162; a system of an active halogenand 3-keto substituted cumarin compound in Japanese Patent Kokai No.58-15503, corresponding to U.S. Pat. No. 4,505,793; a system of 3-ketosubstituted cumarin and N-phenylglycine in Japanese Patent Kokai No.56-460, corresponding to U.S. Pat. No. 4,278,751 a combination of3-substituted cumarin and a quinazolinone derivative in Japanese PatentKokai No. 61-97650 and hexaarylbisimidazole and 3-keto substitutedcumarin in Japanese Patent Kokai No. 61-123603.

However, the above photopolymerization initiator systems do not havesufficient sensitivity and, therefore, for exposure to light at a highspeed by means of a low power laser it is required to find a moresensitive photopolymerization initiator.

OBJECTS OF THE INVENTION

The main object of the present invention is to further improvesensitivity of a photopolymerizable composition up to a visible lightray.

This object as well as other objects and advantages will become apparentto those skilled in the art from the following description.

SUMMARY OF THE INVENTION

According to the present invention, there is provided aphotopolymerizable composition which comprises:

(a) at least one ethylenic unsaturated compound which is non-gaseous atroom temperature;

(b) at least one metallic arene compound of the general formula (I):

    [ (R.sup.1) (R.sup.2 M)].sup.m+ Y.sup.n-                   (I)

m and n are an integer of 1 or 2, R¹ is π-arene, R² is π-arene or ananion of π-arene, M is a monovalent to trivalent metallic cation of theIVb to VIIb group, VIII group or Ib group of the periodic table, and Yis an anion selected from the group consisting of BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻,SbF₆ ⁻, FeCl₄ ⁻, SnCl₆ ⁻, SbCl₆ ⁻ and BiCl₆ ⁻ ; and

(c) at least one compound selected from the group consisting of ap-aminophenyl unsaturated ketone compound of the general formula (II):##STR1## wherein m and n are 0 or 1, R³ and R⁴ are hydrogen atom or analkyl group having 1 to 6 carbon atoms, or CH₂ COOR⁸ (wherein R⁸ ishydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkalinemetal, ammonium or an amine), or C₂ H₄ CF₃, C₂ H₄ I, C₂ H₄ Br, C₂ H₄ Cl,C₂ H₄ F, C₂ H₄ CN or C₂ H₄ NO₂, R⁵ is methylidine or an alkylene-iridingroup having 1 to 6 carbon atoms which may combine with R⁶ and form aring together with the carbonyl group, R⁶ is carbon atom, anunsubstituted phenyl group or a substituted phenyl group with asubstituent selected from amino, N-alkylamino having 1 to 6 carbonatoms, N,N dialkylamino having 1 to 6 carbon atoms, hydroxy, alkoxyhaving 1 to 6 carbon atoms, alkylthio having 1 to 6 carbon atoms, arylhaving 6 to 14 carbon atoms exemplified by phenyl and naphthyloptionally substituted with alkyl groups of 1 to 4 carbon atoms ormercapto, or a group which forms indanone or tetralone together with R⁵and the carbonyl group, and R⁷ is: ##STR2## (wherein n is 0 or 1, and R⁹and R¹⁰ are hydrogen atom or an alkyl group having 1 to 6 carbon atomsor CH₂ COOR¹¹ (wherein R¹¹ is hydrogen atom, an alkyl group having 1 to6 carbon atoms, an alkaline metal, ammonium, or an amine), or C₂ H₄ CF₃,C₂ H₄ I, C₂ H₄ Br, C₂ H₄ Cl, C₂ H₄ F, C₂ H₄ CN or C₂ H₄ NO₂),

a pyridine derivative of the general formula (III): ##STR3## wherein nis 1 or 2, and R¹² and R¹³ are an alkyl group having 1 to 6 carbon atomsand A is an optionally present aryl group, which can be condensed to thepyridine ring to form a quinoline ring, or a salt thereof, and

a xanthene or thioxanthene compound of the general formula (IV):##STR4## wherein D is oxygen atom or sulfur atom, X' is hydrogen atom orhalogen atom, Y is carbon atom or nitrogen atom, provided that, when Yis carbon atom, Y is bonded to the adjacent carbon atom through a doublebonding (the dotted line part) and, when Y is nitrogen atom, Y is bondedto the adjacent carbon atom through a single bond, Z is oxygen atom (inthis case, Z is bonded to the adjacent carbon atom through a doublebond), an alkoxy group having 1 to 6 carbon atoms or an alkanoyloxygroup having 1 to 6 carbon atoms, R¹⁴ is an alkyl group having 1 to 6carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, analkoxyalkyl group having 2 to 12 carbon atoms, a dialkylaminoalkyl grouphaving 3 to 18 carbon atoms, or an aryl group of 6-14 carbon atoms,exemplified by phenyl and naphthyl optionally substituted with alkylgroups of 1-4 carbon atoms, and R¹⁵ is hydrogen atom, an alkoxy grouphaving 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms ora dialkylamino group having 1 to 6 carbon atoms.

Optionally, the photopolymerizable composition of the present inventionfurther includes:

(d) at least one compound selected from the group consisting of acompound of the general formula (V): ##STR5## wherein R¹⁶, R¹⁸ and R¹⁹are the same or different and are hydrogen, an alkyl group having 1 to 6carbon atoms, an alkoxy group having 1 to 6 carbon atoms, cyano,carboxylic acid alkyl ester wherein the alkyl group has 1 to 4 carbonatoms, carboxylic acid alkyl amide wherein the alkyl group has 1 to 4carbon atoms, nitro or halogen, or R¹⁶ may form a condensed polycyclicgroup together with the benzene ring (e.g., naphthalene ring, etc.), Xis S, Se or N-R²⁰, R²⁰ is hydrogen or an alkyl group having 1 to 6carbon atoms, R¹⁷ is hydrogen, an alkyl group having 1 to 6 carbon atomsor phenyl or R¹⁷ --(C═CH)_(n) --X-- may form a 5 membered ring condensedwith the benzene ring (e.g., indole ring, etc.), and n is 0 or 1, and

a cyclic diketone compound of the general formula (VI): ##STR6## whereinR²¹ is hydrogen, a substituted or unsubstituted alkyl group having 1 to12 carbon atoms or an aralkyl group of 7-20 carbon atoms the aryl moietyof which has 6 to 10 carbon atoms (e.g., phenyl or naphthyl), and thealkyl moiety of which has 1 to 10 carbon atoms and wherein the arylmoiety is optionally substituted with alkyl of 1 to 4 carbon atoms, G isa bivalent organic group.

Where R⁶ is a substituted phenyl group, the substituent is amino,N-alkylamino having 1 to 6 carbon atoms, N,N-dialkylamino wherein thealkyl groups have 1 to 6 carbon atoms, hydroxy, alkoxy of 1 to 6 carbonatoms, 1 to 6 carbon alkylthio, mercapto and C₆ -C₁₄ -aryl such asphenyl or naphthyl optionally substituted with alkyl of 1 to 4 carbonatoms.

DETAILED DESCRIPTION OF THE INVENTION

The ethylenic unsaturated compound used in the present invention is amonomer suitable for a chain growth addition reaction initiated by afree radical. Examples thereof include pentaerythritol triacrylate,polyethylene glycol diacrylate, triethylene glycol diacrylate,polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate,trimethylolpropane triacrylate, trimethylolpropane trimethacrylate andthe like. They can be used alone or in combination thereof.

The second component (b) is a metallic arene compound represented by thegeneral formula (I). Examples thereof include metallic arene compoundsdisclosed in EP-A 94914, EP-A 109851 and EP-A 152377 as photo-cationicpolymerization initiators. As π-arene of R¹ and R², for example, thereare aromatic groups having 6 to 24 carbon atoms and hetero aromaticgroups having 3 to 30 carbon atoms, and these groups may be mononuclear,condensed polynuclear or uncondensed polynuclear groups. They may beunsubstituted, or may be monosubstituted or polysubstituted with thesame or different substituents, for example, an alkyl group having 1 to12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, analkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 8carbon atoms, cyano group, an alkylthio group having 1 to 6 carbonatoms, phenoxy group, a monocarboxylic acid group having 2 to 6 carbonatoms or its ester or amide group, phenyl group, alkanoyl group having 2to 5 carbon atoms, ammonium group, pyridinium group, nitro group,alkylsufinyl group having 1 to 6 carbon atoms, alkylsulfonyl grouphaving 1 to 6 carbon atoms and sulfamoyl group having 2 to 5 carbonatoms; halogen atom (e.g., chlorine, bromine, fluorine, iodine, etc.)and the like.

As the metallic arene compound, that having a small reduction potentialis preferred because it provides high sensitivity to thephotopolymerizable compound. Accordingly, the compound having anelectron attractive substituent or a polycyclic group is particularlypreferred. Examples of suitable π-arene include benzene, toluene,xylene, ethylbenzene, dimethoxybenzene, p-chlorotoluene, chlorobenzene,bromobenzene, acetylbenzene, benzoic acid, ethyl benzoate, naphthalene,chloronaphthalene, bromonaphthalene, pyrene, naphthacene, thiophene,chromen, benzothiophene, xanthene, thioxanthene, carbazole and the like.As the anion of π-arene of R², there are anions of the above π-arenes,for example, indenyl anion and, particularly, cyclopentadienyl anion,and these anions may be unsubstituted or may be monosubstituted orpolysubstituted with the same or different substituents as describedabove. In this case, an electron attractive substituent is particularlypreferred. Examples of suitable anions of π-arene include anion ofcyclopentadiene, anions of methyl-, ethyl-, n-propyl- andn-butylcyclopentadiene, anion of dichlorocyclopentadiene, anions ofcyclopentadiene carboxylic acid and alkyl esters thereof and anions ofacetylcyclopentadiene, cyclocyclopentadiene and benzoylcyclopentadiene.

M is a monovalent to trivalent metallic cation of from the IVb to VIIbgroup, VIII group or Ib group of the periodic table, for example,titanium, zirconium, hafnium, vanadium, niobium, chrome, molybdenum,tungsten, manganese, rhenium, iron, cobalt, nickel, copper and the like.Chromium, cobalt, manganese, tungsten, iron and molybdenum arepreferred. Particularly, a cation of iron is most preferred.

Examples of Y include BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, FeCl₄ ⁻, SnCl₆ ²⁻,SbCl₆ ⁻, BiCl₆ ⁻ and the like. Most preferable anion is SbF₆ ⁻, BF₄ ⁻,AsF₆ ⁻ and PF₆ ⁻.

The compound of the formula (I) can be synthesized according to a knownmethod. Particularly, as iron arene compounds, many kinds of compoundsare disclosed in Chemiker-Zeitung, 108 (11) 345-354 (1984).

Examples of such compounds include (η⁶ -benzene) (η⁵-cyclopentadienyl)iron(II) hexafluorophosphate, (η⁶ -toluene)(η⁵-cyclopentadienyl)iron(II) hexafluorophosphate, (η⁶-cumene)(η-cyclopentadienyl)iron(II) hexafluorophosphate, (η⁶-benzene)(η⁵ -cyclopentadienyl)iron(II) tetrafluoroborate, (η⁶-naphthalene)(η⁵ -cyclopentadienyl)iron(II) hexafluorophosphate, (η⁶-anthracene)(η⁵ -cyclopentadienyl)iron (II) hexafluorophosphate, (η⁶-pyrene)(η⁵ -cyclopentadienyl)iron(II) tetrafluoroborate, (η⁶ -benzene)(η⁵ -cyanocyclopentadienyl)iron(II) hexafluorophophate, (η⁶ -cumene)(η⁵-chlorocyclopentadienyl)iron(II) tetrafluoroborate, (η⁶ benzene) (η⁵-carboethoxycyclohexadienyl)iron(II) hexafluorophosphate, (η⁶-benzene)(η⁵ -1,3-dichlorocyclohexadienyl)iron(II) hexafluorophosphate,(η⁶ -cyanobenzene)(η⁵ -cyclohexadienyl)iron(II) hexafluoro-phosphate,(η⁶ -acetophenone)(η⁵ -cyclopentadienyl)iron(II) hexafluorophosphate,(η⁶ -benzenesulfonamide) (η⁵ -cyclopentadienyl)iron(II)tetrafluoroborate, (η⁶ -chloronaphthalene)(η⁵ -cyclopentadienyl)iron(II)hexafluorophosphate, (η⁶ -anthracene)(η⁵ -cyanocyclopentadienyl)iron(II)hexafluorophosphate and the like. These compounds can be synthesizedaccording to a method disclosed in Dokl. Akd. Nauk SSSR, 149, 615(1963).

Examples of the other metal arene compounds include (η⁶ -benzene)(η⁵-cyclopentadienyl)cobalt(III) bis(tetrafluoroborate), (η⁶ -benzene)(η⁵-cyclopentadienyl)cobalt(II) hexafluorophosphate, (η⁶ -cyanobenzene)(η⁵-cyclopentadienyl)cobalt(II) tetrafluoroborate, bis(η⁵-cyclopentadienyl)cobalt(III) hexafluorophophate, bis(η⁵-chlorocyclopentadienyl)nickel(II) hexafluoroantimonate,(η7-cycloheptatrienyl) (η⁵ -cyclopentadienyl)manganese(III)hexafluorophosphate, (η⁸ -cyclooctatetrenyl)(η⁵-cyclopentadienyl)chrome(III) hexafluorophophate and the like.

The compounds of the component (b) can be used alone or in combinationthereof.

Examples of p-aminophenyl unsaturated ketone compound as the thirdcomponent (c) represented by the general formula (II) include2,5-bis(4'-diethylaminobenzylidene)cyclopentanone,2,5-bis(4'-dimetylaminobenzylidene)cyclopentanone, 2,6-bis(4-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4-dimethylaminobenzylidene)cyclohexanone,2,5-bis(4'-dimethylaminocinnamylidene)cyclopentanone,2,6-bis(4'-dimethylaminocinnamylidene)cyclohexanone,1,3-bis(4'-dimethylaminobenzylidene)acetone,2-(4'-diethylaminobenzylidene)-1-indanone, 2(9'-durolylidene)-1-indanone,2-(4'-diethyl-aminobenzylidene)-1-tetralone,4'-diethylamino-2'-methylbenzylideneacetophenone,2,5-bis(4'-N-ethyl-N-carbomethoxymethylaminobenzylidene)cyclopentanone,2,5-bis(4'-N-ethyl-N-carboxymetylaminobenzylidene) pentanone and sodiumsalt thereof,2,5-bis(4'-N-methyl-N-cyanoethylaminobenzylidene)cyclopentanone,2,5-bis(4'-N-ethyl-N-chloroethylaminocinnamylidene)cyclopentanone,2,6-bis(4'-N-cyanoethylaminobenzylidene)cyclohexanone,2-(4'-N-ehtyl-N-carboxymethylaminobenzylidene)-1-indanone, sodium saltof 2-(4'-N-ethyl-N-carboxymethylaminobenzylidene)-1-tetralone,2-((4'-ethyl-N-cyanoethylaminobenzylidene)-1-indanone and the like.

Particularly preferred compounds are p-aminophenyl compound of theformula (II) wherein at least one of R³, R⁴, R⁹ and R¹⁰ is CH₂ COOR¹¹(wherein R¹¹ is alkyl group having 1 to 6 carbon atoms), CH₂ COOH oralkaline metal salt, ammonium salt or amine salt thereof, or C₂ H₄ CF₃,C₂ H₄ I, C₂ H₄ Cl, C₂ H₄ F, C₂ H₄ CN or C₂ H₄ NO₂.

Examples of the pyridine derivative conjugated with a dialkylaminophenylgroup as the third component (c) represented by the general formula(III) include 4-(p-dimethylaminostyryl)pyridine,4-(p-diethylaminostyryl)pyridine, 2-(p-dimethylaminostyryl)pyridine,2-(p-diethylaminostyryl)pyridine, 4-(p-dimetylaminostyryl)quinoline,4-(p-diethylaminostyryl)quinoline, 2-(p-dimethylaminostyryl)quinoline,2-(p-diethylaminostyryl)quinoline,2-(p-diethylaminostyryl)-6-ethoxyquinoline,4-(p-dimethylaminostyryl)pyridinium hydrochloride,4-(p-dimethylaminostyryl)quinolinium hydrobromide,2-(p-dimethylaminostyryl) quinolinium hexafluorophosphate and the like.

Examples of the xanthene or xanthene compound as the third component (c)represented by the general formula (IV) include those wherein X' ishydrogen, chlorine, bromine or the like, Z is methoxy, ethoxy, propoxy,acetyloxy, propionyloxy or the like, R¹⁴ is methyl, ethyl, propyl,hydroxymethyl, hydroxyethyl, methoxymethyl, methoxyethyl,dimethylaminomethyl, diethylaminopropyl, phenyl, xylyl, tolyl, anisyl orthe like, R¹⁵ is hydrogen, methoxy, ethoxy, methyl, ethyl, propyl,dimethylamino, diethylamino or the like.

The compounds of the component (c) can be used alone or in combinationthereof.

In the present invention, when the compounds represented by the formulas(V) and/or (VI) of the component (d) are added, sensitivity of thecomposition is further improved. Examples of the compound represented bythe general formula (V) include N-phenylglycine,N-(p-methylphenyl)glycine, N-(p-methoxyphenyl)glycine,N-(p-cyanophenyl)glycine, N-(p-chlorophenyl)glycine,N-methyl-N-phenylglycine, indoleacetic acid, N-methylindoleacetic acid,6-cyanoindoleactic acid and the like.

The cyclic diketone compound represented by the general formula (VI) isa cyclic β-dicarbonyl compound having an active methylene group with anunstable hydrogen atom. In the formula (VI), R²¹ is hydrogen, anunsubstituted or substituted alkyl group or aralkyl group of 7 to 20carbon atoms and G is a bivalent organic group which may contain one ormore hetero atoms and may contain one or more substituents on either orboth carbon and hetero atoms thereof. The above alkyl group is thathaving 1 to 12 carbon atoms and, as the substituted alkyl, for example,there are hydroxylalkyl, cyanoalkyl, haloalkyl, alkoxyalkylene,alkylenethioether, aryloxyalkylene and the like. The aryl hydrocarbonmoiety of the above aralkyl has 6 to 10 carbon atoms and is exemplifiedby phenyl or naphthyl. The above bivalent organic group G completes thering shown. This part may contain one or more hetero atoms, for example,nitrogen, oxygen and sulfur. Examples of these compounds include 5,5-dimethyl-1,3-cyclohexanedione, 2-methyl-1,3-cyclohexanedione,2-methyl-1,3-cyclopentadione, 2,4-diethyl-1,3-cyclobutanedione,2-methyl-1,3-cyclobutanedione, 5-methyl-2-thiobarbituric acid,barbituric acid, 3-ethyltetronic acid,2,4-dimethyl-3-oxo-5-hydroxy-5-methoxypentenoic acid 8-lactone,1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid,2-methyldimedone, 1,3-indanedione, 2-methylindanedione,bis-[5-(1,3-dimethyl-barbituryl)]methane, 1,5-diphenyl-3-[2-(phenylthio)ethyl]-2,4-pyrrolidinedione,1-phenyl-3,5-diketo-4-n-butyltetrahydropyrazole,2,2-dimethyl-m-dioxane-4,6-dione, 2,2,5-trimethyl-m-dioxane-4,6-dioneand the like.

Preferably, a thermoplastic polymeric organic binder can be contained inthe composition of the present invention. Examples of such a polymericbinder include (i) copolyesters composed of terephthalic acid,isophthalic acid, sebasic acid, adipic acid and hexahydroterephthalicacid, (ii) polyamides, (iii) vinylidene chloride copolymers, (iv)ethylene/vinylacetate copolymers, (v) cellulose ethers, (vi)polyethylene, (vii) synthetic rubbers, (viii) cellulose esters, (ix)polyvinyl esters containing polyvinyl acetate/acrylate and polyvinylacetate/methacrylate copolymers, (x) polyacrylate and poly α-alkylacrylate esters, for example, polymethyl methacrylate and polyethylmethacrylate, (xi) high molecular weight ethylene oxide polymers havingweight average molecular weight of 4,000 to 4,000,000 (polyethyleneglycols), (xii) polyvinyl chloride and copolymers thereof, (xiii)polyvinyl acetal, (xiv) polyformaldehyde, (xv) polyurethane, (xvi)polycarbonate, (xvii) polystyrene and the like.

In the most preferred embodiment of the present invention, thephotopolymerizable binder is selected so that, although aphotopolymerizable coating is predominantly soluble in an aqueoussolution, for example, alkaline solution, it becomes realtivelyinsoluble in such a solution after exposure to active ray radiation.Typically, the polymer which satisfies these requirements is acarboxylated polymer, for example, a vinyl addition polymer containingfree carboxylic acid group. As the preferable binder, for example, thereare styrene/maleic anhydride (1:1) copolymer having the acid value ofabout 190 and the weight average molecular weight of about 10,000 whichis partially esterified with an isobutanol mixture, and the combinationof styrene/maleic anhydride copolymer and ethyl acrylate/methylmethacrylate/acrylic acid terpolymer. As other preferred binders, forexample, there are polyacrylate esters and poly α-alkylacrylate esters,particularly, polymethyl methacrylate.

In the composition of the present invention, other known inertadditives, for example, non-polymerizable plasticizers, pigments,fillers and the like can be added so far as they do not interfere withexposure of the photopolymerizable composition to light.

The photopolymerizable composition of the present invention preferablycontains 0.01 to 50 parts by weight, particularly, 0.1 to 30 parts byweight of the component (b) and 0.01 to 20 parts by weight,particularly, 0.1 to 20 parts by weight of the component (c) per 100parts by weight of the component (a). When the component (d) is used,the preferred amount thereof is 0.01 to 20 parts by weight,particularly, 0.1 to 20 parts by weight per 100 parts by weight of thecomponent (a). The binder is preferably used in an amount of 0 to 1,000parts, particularly, 0 to 50 parts by weight per 100 parts by weight ofthe component (a).

The photopolymerizable composition of the present invention can be usedby coating it on various kinds of bases according to a known method.

The term "base" used herein means all natural or synthetic supports,preferably those which can be present in the form of flexible or rigidfilm or sheet. For example, the base may be a metallic sheet or foil,sheet or film of synthetic organic resins, cellulose paper, fiber boardand the like, or a composite material of two or more of thesesubstances. Examples of the specific base include aluminablasted-aluminum, anodized aluminum, aluminum blasted-polyethyleneterephthalate film, polyethylene terephthalate film, for example, resinundercoated-polyethylene terephthalate film, electrostaticdischarged-polyethylene terephthalate film, polyvinyl alcoholcoated-paper, crosslinked polyester coated-paper, nylon, glass,cellulose acetate film and the like.

In general, the base is selected according to the particular purposes.For example, in the case of producing a printed circuit, the base may bea plate of fiber board on which copper has been coated. In the case ofproducing a litho printing plate, the base may be anodized aluminum.

Preferably, a layer of the photopolymerizable composition has athickness of 0.0001 inch (0.00025 cm) to about 0.01 inch (0.025 cm) andis adhered to a thin flexible polymer film support (base), through whichan active radiation can pass and reach the photopolymerizable layer,with a certain degree of or medium adhesion. A protective covering layeror covering sheet can be adhered on it. The latter sheet is adhered insuch a degree that adhesion between it and the photopolymerizable layeris weaker than that between the film support and the photopolymerizablelayer. Particularly preferred support is a transparent polyethyleneterephthalate film having a thickness of about 0.001 inch (0.0025 cm) toabout 0.4 inch (1.0 cm). Polyethylene having a thickness of 0.0005 inch(0.0013 cm) to 0.04 inch (0.10 cm) is a preferred covering sheet andpolyvinyl alcohol coating is a preferred covering layer.

As a normal light source, for example, there are fluorescent tube,mercury vapor lamp, metal addition lamp and arc lamp which provide anarrow or wide waveband of light having mean wavelengths of 405, 436 and546 nm (Hg). As an interference light source, for example, there arepulse type xenon, argon ion, helium-cadmium, ionized neon laser and thelike. Cathode ray tube which generates a visible light ray and is widelyused for a printing-out system is also useful for the composition of thepresent invention. In general, these sources include a phosphorescentmaterial interior coating for generating ultraviolet or visible lightrays as means for converting electric energy into photo energy and anoptical fiber face plate as means for introducing radiation into aphotosensitive target.

The photopolymerizable composition of the present invention has highsensitivity to a visible light ray and, therefore, a light source havinga low energy can be used and a lot of printing plates can be exposed tolight and developed within a given period of time.

Further, the photopolymerizable composition of the present invention hassuch advantages that a light source can be kept away from a printingplate and the light rays are made to be parallel. Therefore, forexample, when an image contains meshes and dots, clear meshes and dotshaving vertical side parts can be formed.

The following Examples and Comparative Examples further illustrate thepresent invention in detail but are not to be construed to limit thescope thereof.

All the "parts" and "%'s" in Examples and Comparative Examples are byweight unless otherwise stated.

Examples 1 to 48 and Comparative Examples 1 to 12

A paint for a photosensitive layer of the following formulation wasapplied on a transparent polyethylene terephalate film of 100 μ inthickness having an undercoating layer and dried at 120° C. for 1 minuteusing a hot-air dryer to obtain a coating film of 3 μ in thickness.Then, aqueous 7 % polyvinyl alcohol solution (completely saponified,polymerization degree: 500) was applied on the film and dried at 100° C.for 1 minute using a hot-air dryer to obtain an overcoated layer of 1 %in thickness to obtain a sensitivity test specimen.

    ______________________________________                                        Formulation of paint                                                          Ingredients              Parts                                                ______________________________________                                        Poly(methyl methacrylate/methacrylic acid)                                                             52                                                   molar ratio: 70/30                                                            Tetraethylene glycol diacrylate                                                                        40                                                   Component (b)             5                                                   Component (c)             3                                                   Methanol                 200                                                  Ethyl acetate            80                                                   Chloroform               120                                                  ______________________________________                                    

A 21/2 step tablet (gray film scale manufactured by Dainippon ScreenMfg. Co., Ltd., Japan) as a negative film was superimposed on the abovesensitivity test specimen and then exposed to light at a distance of 15cm for 5 minutes using a light source (490 nm) combined with a xenonlamp (UXL-500D-O manufactured by Ushio Electric Co., Ltd., Japan), aninterference filter (KL-49 manufactured by Toshiba Co., Ltd., Japan) andthe same colored glass filter Y-45. Then, the specimen was dipped inaqueous 7 % sodium carbonate solution at 30° C. for 10 seconds andrinsed with water to remove the uncured portion and dried. The number ofcompletely cured steps of the 21/2 step tablet was determined. Theresults are shown in Tables 1, 2 and Tables 4 to 7, respectively. Theresults of Comparative Examples are shown in Tables 3 and 8. In Tables 7and 8, "TX-1" means the compound of the formula: ##STR7##

                                      TABLE 1                                     __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c)  Number of steps                            __________________________________________________________________________    1      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-diethylamino-                                                                     11                                                pentadienyl)iron(II) hexa-                                                                 benzylidene)cyclopentanone                                       fluorophosphate                                                        2      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-diethylamino-                                                                     11                                                pentadienyl)iron(II) hexa-                                                                 benzylidene)cyclopentanone                                       fluorophosphate                                                        3      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,6-bis(4'-diethylamino-                                                                     11                                                pentadienyl)iron(II) hexa-                                                                 benzylidene)cyclopentanone                                       fluorophosphate                                                        4      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2-(4'-diethylaminobenzylidene)-                                                              10                                                pentadienyl)iron(II) hexa-                                                                 1-indanone                                                       fluorophosphate                                                        5      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2-(4'-diethylaminobenzylidene)-                                                              10                                                pentadienyl)iron(II) hexa-                                                                 1-tetralone                                                      fluorophosphate                                                        6      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-dibutylamino-                                                                     11                                                pentadienyl)iron(II) hexa-                                                                 benzylidene)cyclopentanone                                       fluorophosphate                                                        7      (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis(4'-diethylamino-                                                                     11                                                pentadienyl)iron(II) hexa-                                                                 benzylidene)cyclopentanone                                       fluorophosphate                                                        __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c)    Number of steps                          __________________________________________________________________________     8     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-N-ethyl-N-carbo-                                                                    12                                              pentadienyl)iron(II) hexa-                                                                 methoxymethylaminobenzyliden)-                                   fluorophosphate                                                                            cyclopentanone                                             9     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'N-ethyl-N-carbo-                                                                     14                                              pentadienyl)iron(II) hexa-                                                                 methoxymethylaminobenzyliden)-                                   fluorophosphate                                                                            cyclopentanone                                            10     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  sodium salt of 2,5-bis(4'-N-                                                                   14                                              pentadienyl)iron(II) hexa-                                                                 ethyl-N-carboxy-methylamino-                                     fluorophosphate                                                                            benzylidene)cyclopentanone                                11     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-N-ethyl-N-cyanoethyl-                                                               12                                              pentadienyl)iron(II) hexa-                                                                 aminobenzylidene)cyclopentanone                                  fluorophosphate                                                        12     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-N-butyl-N-cyanoethyl-                                                               12                                              pentadienyl)iron(II) hexa-                                                                 aminobenzylidene)cyclopentanone                                  fluorophosphate                                                        13     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,6-bis(4'-N-ethyl-N-carboxy-                                                                  12                                              pentadienyl)iron(II) hexa-                                                                 methylaminobenzylidene)cyclo-                                    fluorophosphate                                                                            hexanone                                                  14     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  2,5-bis(4'-N-ethyl-N-carboxy-                                                                  14                                              pentadienyl)iron(II) hexa-                                                                 methylaminocinnamylidene)cyclo-                                  fluorophosphate                                                                            pentanone                                                 __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    Comp.                                                                         Example No.                                                                          Component (b)                                                                              Component (c)  Number of steps                            __________________________________________________________________________    1      2,2'-(0-chlorophenyl)-                                                                     2,5-bis(4'-diethylamino-                                                                     6                                                 4,4',5,5'-tetraphenylbis-                                                                  benzylidene)cyclopentanone                                       imidazole                                                              2      1,3,5-tris(trichloromethyl)-                                                               2,5-bis(4'-diethylamino-                                                                     9                                                 S-triazine   benzylidene)cyclopentanone                                3      none         2,5-bis(4'-diethylamino-                                                                     0                                                              benzylidene)cyclopentanone                                4      (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  none           0                                                 pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Example No.                                                                          Component (b) Component (c)                                                                             Number of steps                              __________________________________________________________________________    15     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                  4-(p-diethylaminostyryl)-                                                                 12                                                  cyclopentadienyl)iron(II)                                                                   quinoline                                                       hexafluorophosphate                                                    16     (η.sup.6 -benzene)(η.sup.5 -acetyl-                                                 4-(p-diethylaminostyryl)-                                                                 12                                                  cyclopentadienyl)iron(II)                                                                   quinoline                                                       hexafluorophosphate                                                    17     (η.sup.6 -benzene)(η.sup.5 -acetyl-                                                 4-(p-diethylaminostyryl)-                                                                 11                                                  cyclopentadienyl)iron(II)                                                                   quinoline                                                       hexafluorophosphate                                                    18     (η.sup.6 -cyanobenzene)(η.sup.5 -                                                   4-(p-diethylaminostyryl)-                                                                 12                                                  cyclopentadienyl)iron(II)                                                                   quinoline                                                       hexafluorophosphate                                                    19     (η.sup.6 -methylbenzoate)(η.sup.5 -                                                 4-(p-diethylaminostyryl)-                                                                 12                                                  cyclopentadienyl)iron(II)                                                                   quinoline                                                       hexafluorophosphate                                                    20     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                  4-(p-diethylaminostyryl)-                                                                 11                                                  cyclopentadienyl)iron(II)                                                                   quinoline                                                       hexafluorophosphate                                                    21     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                  4-(p-diethylaminostyryl)-                                                                 12                                                  chlorocyclopentadienyl)iron                                                                 quinoline                                                       (II) hexafluorophosphate                                               __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c)  Number of steps                            __________________________________________________________________________    22     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                 2,5-bis(4'-diethylamino-                                                                     14                                                cyclopentadienyl)iron(II)                                                                  benzylidene)cyclopentanone                                       hexafluorophosphate                                                    23     (η.sup.6 -benzene)(η.sup.5 -acetyl-                                                2,5-bis(4'-diethylamino-                                                                     14                                                cyclopentadienyl)iron(II)                                                                  benzylidene)cyclopentanone                                       hexafluorophosphate                                                    24     (η.sup.6 -benzene)(η.sup.5 -chloro-                                                2,5-bis(4'-diethylamino-                                                                     13                                                cyclopentadienyl)iron(II)                                                                  benzylidene)cyclopentanone                                       hexafluorophosphate                                                    25     (η.sup.6 -cyanobenzene)(η.sup.5 -                                                  2,5-bis(4'-diethylamino-                                                                     14                                                cyclopentadienyl)iron(II)                                                                  benzylidene)cyclopentanone                                       hexafluorophosphate                                                    26     (η.sup.6 -methylbenzoate)(η.sup.5 -                                                2,5-bis(4'-diethylamino-                                                                     14                                                cyclopentadienyl)iron(II)                                                                  benzylidene)cyclopentanone                                       hexafluorophosphate                                                    27     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                 2,5-bis(4'-diethylamino-                                                                     13                                                cyclopentadienyl)iron                                                                      benzylidene)cyclopentanone                                       (II)hexafluorophosphate                                                28     (η.sup.5 -chlorobenzene)(η.sup.5 -                                                 2,5-bis(4'-diethylamino-                                                                     14                                                chlorocyclopentadienyl)iron                                                                benzylidene)cyclopentanone                                       (II)hexafluorophosphate                                                __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c)  Number of steps                            __________________________________________________________________________    29     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  1,1'-dicyano-4-(p-dimethyl-                                                                  11                                                pentadienyl)iron(II) hexa-                                                                 aminophenyl)-1,3-butadiene                                       fluorophosphate                                                        30     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  1,1'-dicyano-4-(p-diethyl-                                                                   12                                                pentadienyl)iron(II) hexa-                                                                 aminophenyl)-1,3-butadiene                                       fluorophosphate                                                        31     (η.sup.6 -cumene)(η.sup.5 -cyclo-                                                  1,1'-dicyano-4-(o-methyl-                                                                    11                                                pentadienyl)iron(II) hexa-                                                                 p-dimethylaminophenyl)-1,3-                                      fluorophosphate                                                                            butadiene                                                 32     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 1,1'-dicyano-4-(p-dimethyl-                                                                  11                                                pentadienyl)iron(II) hexa-                                                                 aminophenyl)-1,3-butadiene                                       fluorophosphate                                                        __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    Example No.                                                                          Component (b)  Component (c)  Number of steps                          __________________________________________________________________________    33     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                   4-(p-diethylaminostyryl)                                                                     8                                               pentadienyl)cobalt(II)                                                                       quinoline                                                      hexafluorophosphate                                                    34     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                   2,5-bis(4'-diethylamino-                                                                     10                                              pentadienyl)cobalt(II)                                                                       benzylidene)cyclopentanone                                     hexafluorophosphate                                                    35     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                     TX-1         9                                               pentadienyl)cobalt(II)                                                        hexafluorophosphate                                                    36     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                   1,1'-dicyano-4-(p-dimethyl-                                                                  8                                               pentadienyl)cobalt(II)                                                                       aminophenyl)-1,3-butadiene                                     hexafluorophosphate                                                    37     bis(η.sup.5 -chloropentadienyl)                                                          4-(p-diethylaminostyryl)-                                                                    7                                               nickel(II)hexafluorophosphate                                                                quinoline                                               38     bis(η.sup.5 -chloropentadienyl)                                                          2,5-bis(4'-diethylamino-                                                                     9                                               nickel(II)hexafluorophosphate                                                                benzylidene)cyclopentanone                              39     bis(η.sup.5 -chloropentadienyl)                                                            TX-1         8                                               nickel(II)hexafluorophosphate                                          40     bis(η.sup.5 -chloropentadienyl)                                                          1,1'-dicyano-4-(p-dimethyl-                                                                  6                                               nickel(II)hexafluorophosphate                                                                aminophenyl)-1,3-butadiene                              41     (η.sup.7 -cycloheptatrienyl)                                                             4-(p-diethylaminostyryl)                                                                     7                                               (η.sup.5 -cyclopentadienyl)                                                              quinoline                                                      manganese(III)hexafluoro-                                                     phosphate                                                              42     (η.sup.7 -cycloheptatrienyl)                                                             2,5-bis(4'-diethylamino-                                                                     9                                               (η.sup.5 -cyclopentadienyl)                                                              benzylidene)cyclopentanone                                     manganese(III)hexafluoro-                                                     phosphate                                                              43     (η.sup.7 -cycloheptatrienyl)                                                               TX-1         8                                               (η.sup.5 -cyclopentadienyl)                                               manganese(III)hexafluoro-                                                     phosphate                                                              44     (η.sup.7 -cycloheptatrienyl)                                                             1,1'-dicyano-4-(p-dimethyl-                                                                  6                                               (η.sup.5 -cyclopentadienyl)                                                              aminophenyl)-1,3-butadiene                                     manganese(III) hexafluoro-                                                    phosphate                                                              45     (η.sup.8 -cycloctatetrenyl)                                                              4-(p-diethylaminostyryl)                                                                     8                                               (η.sup.5 -cyclopentadienyl)                                                              quinoline                                                      chrome(III) hexafluoro-                                                       phosphate                                                              46     (η.sup.8 -cycloctatetrenyl)                                                              2,5-bis(4'-diethylamino-                                                                     10                                              (η.sup.5 -cyclopentadienyl)                                                              benzylidene)cyclopentanone                                     chrome(III) hexafluoro-                                                       phosphate                                                              47     (η.sup.8 -cycloctatetrenyl)                                                                TX-1         9                                               (η.sup.5 -cyclopentadienyl)                                               chrome(III) hexafluoro-                                                       phosphate                                                              48     (η.sup.8 -cycloctatetrenyl)                                                              1,1'-dicyano-4-(p-dimethyl-                                                                  8                                               (η.sup.5 -cyclopentadienyl)                                                              aminophenyl)-1,3-butadiene                                     chrome(III) hexafluoro-                                                       phosphate                                                              __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________    Comp.                                                                         Example No.                                                                          Component (b)   Component (c) Number of steps                          __________________________________________________________________________    5      (η.sup.6 -benzene)(η.sup.5 -cyano-                                                      none        0                                               cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    6      (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                      none        0                                               pentadienyl)cobalt(II) hexa-                                                  fluorophosphate                                                        7      bis(η.sup.5 -chloropentadienyl)                                                             none        0                                               cyclopentadienyl)manganese (III)                                              hexafluorophosphate                                                    8      (η.sup.7 -cycloheptatrienyl)(η.sup.5 -                                                  none        0                                               cyclopentadienyl)manganese (III)                                              hexafluorophosphate                                                    9      (η.sup.8 -cyclooctatetrenyl)(η.sup.5 -                                                  none        0                                               cyclopentadienyl)chrome(III)                                                  hexafluorophosphate                                                    10       none          4-(p-diethylaminostyryl)-                                                                   0                                                               quinoline                                              11       none            TX-1        0                                        12       none          1,1'-dicyanol-4-(p-dimethyl-                                                                0                                                               aminophenyl)-1,3-butadiene                             __________________________________________________________________________

As is clear from Table 1 to Table 8, Examples 1 to 48 of the presentinvention have higher sensitivity to the light source of 490 nm incomparison with Comparative Examples 1 to 12.

Examples 49 to 78

According to the same manner as described in Example 1, each sensitivitytest specimen was obtained except that the component (d) (3 parts) wasfurther added. Test results are shown in Tables 9 to 11.

                                      TABLE 9                                     __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c)                                                                             Component (d)                                                                           Number of steps                     __________________________________________________________________________    49     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  N-phenylglycine                                                                         16                                         pentadienyl)iron(II) hexa-                                                                 quinoline                                                        fluorophosphate                                                        50     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  N-(p-methylphenyl)                                                                      15                                         pentadienyl)iron(II) hexa-                                                                 quinoline   glycine                                              fluorophosphate                                                        51     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  N-(p-cyanophenyl)                                                                       18                                         pentadienyl)iron(II) hexa-                                                                 quinoline   glycine                                              fluorophosphate                                                        52     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  6-cyanoindoleacetic                                                                     17                                         pentadienyl)iron(II) hexa-                                                                 quinoline   acid                                                 fluorophosphate                                                        53     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  5,5-dimethyl-1,3-                                                                       14                                         pentadienyl)iron(II) hexa-                                                                 quinoline   cyclohexanedione                                     fluorophosphate                                                        54     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  2-methyl-1,3-                                                                           18                                         pentadienyl)iron(II) hexa-                                                                 quinoline   cyclohexanedione                                     fluorophosphate                                                        55     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  2-methyl-1,3-                                                                           17                                         pentadienyl)iron(II) hexa-                                                                 quinoline   cyclopentadione                                      fluorophosphate                                                        56     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  1,3,5-trimethyl                                                                         18                                         pentadienyl)iron(II) hexa-                                                                 quinoline   barbituric acid                                      fluorophosphate                                                        57     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  1,3-indanedione                                                                         16                                         pentadienyl)iron(II) hexa-                                                                 quinoline                                                        fluorophosphate                                                        58     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl)                                                                  2-methyl-1,3-                                                                           18                                         pentadienyl)iron(II) hexa-                                                                 quinoline   indanedione                                          fluorophosphate                                                        __________________________________________________________________________

                                      TABLE 10                                    __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c) Component (d)                                                                            Number of steps                  __________________________________________________________________________    59     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   N-phenylglycine                                                                          18                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                      fluorophosphate                                                        60     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   N-(p-methylphenyl)                                                                       17                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 glycine                                            fluorophosphate                                                        61     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   N-(p-cyanophenyl)                                                                        20                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 glycine                                            fluorophosphate                                                        62     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   6-cyanoindoleacetic                                                                      19                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 acid                                               fluorophosphate                                                        63     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   5-5-dimethyl-1,3-                                                                        16                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 cyclohexanedione                                   fluorophosphate                                                        64     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   2-methyl-1,3-cyclo-                                                                      20                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 hexanedione                                        fluorophosphate                                                        65     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   2-methyl-1,3-cyclo-                                                                      19                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 pentadione                                         fluorophosphate                                                        66     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   1,3,5-trimethyl-                                                                         20                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 barbituric acid                                    fluorophosphate                                                        67     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   1,3-indanedione                                                                          18                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                      fluorophosphate                                                        68     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-diethylamino-                                                                   2-methyl-1,3-indane-                                                                     20                                      pentadienyl)iron(II) hexa-                                                                 benzylidene) cyclopentanone                                                                 dione                                              fluorophosphate                                                        __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c) Component (d)                                                                          Number of steps                    __________________________________________________________________________    69     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 7-diethylamino-3 (2-                                                                        N-phenylglycine                                                                        18                                        pentadienyl)iron(II) hexa-                                                                 benzothiazyl) cumarin                                            fluorophosphate                                                        70     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 3,3'-carbonylbis(7-                                                                         "        18                                        pentadienyl)iron(II) hexa-                                                                 diethylaminocumarin)                                             fluorophosphate                                                        71     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 4-(p-diethylaminostyryl                                                                     "        15                                        pentadienyl)iron(II) hexa-                                                                 pyridine                                                         fluorophosphate                                                        72     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2-(p-diethylaminostyryl)                                                                    "        16                                        pentadienyl)iron(II) hexa-                                                                 quinoline                                                        fluorophosphate                                                        73     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,6-bis(4'-diethylamino-                                                                    "        18                                        pentadienyl)iron(II) hexa-                                                                 benzylidene)cyclohexanone                                        fluorophosphate                                                        74     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 2,5-bis (4'-N-ethyl-N-                                                                      "        18                                        pentadienyl)iron(II) hexa-                                                                 carbomethoxymethylamino-                                         fluorophosphate                                                                            benzylidene) cyclopentanone                               75     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                 7-diethylamino-3-(2-benz-                                                                   "        20                                        cyclopentadienyl)iron(II)                                                                  imidazolyl) cumarin                                              hexafluorophosphate                                                    76     (η.sup.6 -cyanobenzene)(η.sup.5 -                                                  7-diethylamino-3-(2-benz-                                                                   "        20                                        cyclopentadienyl)iron (II)                                                                 imidazolyl) cumarin                                              hexafluorophosphate                                                    77     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                 7-diethylamino-3-(2-benz-                                                                   "        19                                        cyclopentadienyl)iron (II)                                                                 imidazolyl) cumarin                                              hexafluorophosphate                                                    78     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                 7-diethylamino-3-(2-benz-                                                                   "        20                                        cyclopentadienyl)iron                                                                      imidazolyl) cumarin                                              (II) hexafluorophosphate                                               __________________________________________________________________________

Examples 79 to 103 and Comparative Examples 13 to 20

According to the same manner as described in Example 1, each sensitivitytest specimen was obtained except that TX-1 or the following TX-2, X-1or X-2 was used instead of the component (c). Test results are shown inTables 12 to 15. ##STR8##

                                      TABLE 12                                    __________________________________________________________________________    Example No.                                                                          Component (b)   Component (c)                                                                          Component (d)                                                                          Number of steps                      __________________________________________________________________________    79     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                    TX-1     none     13                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    80     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                    TX-2     "        13                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    81     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                      X-1    "        13                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    82     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                      X-2    "        13                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    83     (η.sup.6 -benzene)(η.sup.5 -cyano-                                                    TX-1     "        15                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    84     (η.sup.6 -cyanobenzene)(η.sup.5 -                                                     "        "        15                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    85     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                    "        "        14                                          cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    86     (η.sup.6 -chlorobenzene)(η.sup.5 -                                                    "        "        15                                          cyanocyclopentadienyl)iron(II)                                                hexafluorophosphate                                                    __________________________________________________________________________

                                      TABLE 13                                    __________________________________________________________________________    Example No.                                                                          Component (b)                                                                              Component (c)                                                                          Component (d)                                                                            Number of steps                       __________________________________________________________________________    87     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 TX-1     N-phenylglycine                                                                          13                                           pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        88     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        N-(p-methylphenyl)                                                                       17                                           pentadienyl)iron(II) hexa                                                                           glycine                                                 fluorophosphate                                                        89     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        N-(p-cyanophenyl)                                                                        14                                           pentadienyl)iron(II) hexa-                                                                          glycine                                                 fluorophosphate                                                        90     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        6-cyanoindoleacetic                                                                      15                                           pentadienyl)iron(II) hexa-                                                                          acid                                                    fluorophosphate                                                        91     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        5,5-dimethyl-1,3-                                                                        17                                           pentadienyl)iron(II) hexa-                                                                          cyclohexanedione                                        fluorophosphate                                                        92     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        2-methyl-1,3-cyclo-                                                                      18                                           pentadienyl)iron(II) hexa-                                                                          hexanedione                                             fluorophosphate                                                        93     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        2-methyl-1,3-cyclo-                                                                      19                                           pentadienyl)iron(II) hexa-                                                                          pentanedione                                            fluorophosphate                                                        94     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        1,3,5-trimethylbar-                                                                      19                                           pentadienyl)iron(II) hexa-                                                                          bituric acid                                            fluorophosphate                                                        95     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        1,3-indanedione                                                                          18                                           pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        96     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 "        2-methyl-1,3-indane-                                                                     19                                           pentadienyl)iron(II) hexa-                                                                          dione                                                   fluorophosphate                                                        __________________________________________________________________________

                                      TABLE 14                                    __________________________________________________________________________    Example No.                                                                          Component (b) Component (c)                                                                          Component (d)                                                                          Number of steps                        __________________________________________________________________________     97    (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                  TX-2     N-phenylglycine                                                                        13                                            pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                         98    (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                    X-1    "        17                                            pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                         99    (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                    X-2    "        17                                            pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        100    (η.sup.6 -benzene)(η.sup.5 -cyano-                                                  TX-1     "        19                                            cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    101    (η.sup.6 -benzene)(η.sup.5 -                                                        "        "        19                                            cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    102    (η.sup.6 -chlorobenzene)(η.sup.5 -                                                  "        "        18                                            cyclopentadienyl)iron(II)                                                     hexafluorophosphate                                                    103    (η.sup.6 -chlorobenzene)(η.sup.5 -                                                  "        "        19                                            cyanocyclopentadienyl) iron                                                   (II) hexafluorophosphate                                               __________________________________________________________________________

                                      TABLE 15                                    __________________________________________________________________________    Comp.                                                                         Example No.                                                                          Component (b)                                                                              Component (c)                                                                          Component (d)                                                                           Number of steps                        __________________________________________________________________________    13     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 none     none      0                                             pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        14     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 none     N-phenylglycine                                                                         13                                            pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        15     (η.sup.6 -benzene)(η.sup.5 -cyclo-                                                 none     none      0                                             pentadienyl)iron(II) hexa-                                                    fluorophosphate                                                        16       none       TX-1     none      0                                      17       none       TX-1     N-phenylglycine                                                                         9                                      18       none       TX-1     2-methyl-1,3-cyclo-                                                                     8                                                                   hexanedione                                      19       none       none     N-phenylglycine                                                                         0                                      20       none       none     2-methyl-1,3-cyclo-                                                                     0                                                                   hexanedione                                      __________________________________________________________________________

What is claimed is:
 1. A photopolymerizable composition which (a) atleast one ethylenic unsaturated compound which is non-gaseous at roomtemperature;(b) at least one metallic arene compound of the generalformula (I):

    [R.sup.1)(R.sup.2 M)].sup.m+ Y.sup.n-                      (I)

wherein m and n are an integer of 1 or 2, R¹ is π-arene, R² is π-areneor an anion of π-arene, M is a monovalent to trivalent metallic cationof the IVb to VIIb group, VIII group or Ib group of the periodic table,and Y is an anion selected from the group consisting of BF₄ ⁻, PF₆ ⁻,AsF₆ ⁻, SbF₆ ⁻, FeCl₄ ⁻, SnCl₆ ⁻, SbCl₆ ⁻ and BiCl₆ ⁻ ; and (c) at leastone compound selected from the group consisting of a p aminophenylunsaturated ketone compound of the general formula (II): ##STR9##wherein m and n are 0 or 1, R³ and R⁴ are a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms, or CH₂ COOR⁸ in which R⁸ is a hydrogenatom or an alkyl group having 1 to 6 carbon atoms, an alkaline metal,ammonium or an amine, or C₂ H₄ CF₃, C₂ H₄ I, C₂ H₄ Br, C₂ H₄ Cl, C₂ H₄F, C₂ H₄ CN or C₂ H₄ NO₂, R⁵ is methylidine or an alkylene-iridin grouphaving 1 to 6 carbon atoms which can combine with R⁶ and form a ringtogether with the carbonyl group, R⁶ is carbon atom, a phenyl groupoptionally substituted by an amino, N-alkylamino having to 6 carbonatoms, N,N-dialkylamino having 1 to 6 carbon atoms, hydroxy, alkoxyhaving 1 to 6 carbon atoms, alkylthio having 1 to 6 carbon atoms, arylhydrocarbon having 6 to 14 carbon atoms or mercapto, or a group whichforms indanone or tetralone together with R⁵ and the carbonyl group, andR⁷ is: ##STR10## wherein n is 0 or 1, R⁹ and R¹⁰ are a hydrogen atom oran alkyl group having 1 to 6 carbon atoms or CH₂ COOR¹¹ wherein R¹¹ is ahydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkalinemetal, ammonium, or an amine, or C₂ H₄ CF₃, C₂ H₄ I, C₂ H₄ Br, C₂ H₄ Cl,C₂ H₄ F, C₂ H₄ CN or C₂ H₄ NO₂, a pyridine derivative of the generalformula (III): ##STR11## wherein, n is 1 or 2, R¹² and R¹³ are an alkylgroup having 1to 6 carbon atoms and A is an optionally aryl presentgroup which can be condensed to the pyridine ring to form aquinolinering, or a salt thereof, and a xanthene or thioxanthene compound of thegeneral formula (IV): ##STR12## wherein D is an oxygen atom or a sulfuratom, X' is a hydrogen atom or a halogen atom, Y is a carbon atom or anitrogen atom, provided that, when Y is a carbon atom, Y is bonded tothe adjacent carbon atom through a double bonding indicated by a dottedline in formula (IV), and, when Y is a nitrogen atom, Y is bonded to theadjacent carbon atom through a single bond, Z is an oxygen atom which isbonded to the adjacent carbon atom through a double bond, an alkoxygroup having 1 to 6 carbon atoms or an alkanoyloxy group having 1 to 6carbon atoms, R¹⁴ is an alkyl group having 1 to 6 carbon atoms, ahydroxyalkyl group having 1 to 6 carbon atoms, an alkoxyalkyl grouphaving 2 to 12 carbon atoms, a dialkylaminoalkyl group having 3 to 18carbon atoms, or an aryl hydrocarbon group of 6 to 14 oarbon atomsoptionally substituted with alkyl groups of 1 to 4 carbon atoms, and R¹⁵is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkylgroup having 1 to 6 carbon atoms or a dialkylamino group having 1 to 6carbon atoms.
 2. A photopolymerizable composition according to claim 1,wherein the composition contains 0.01 to 50 parts by weight of thecomponent (b) and 0.01 to 20 parts by weight of the component (c) per100 parts by weight of the component (a).
 3. A photopolymerizablecomposition according to claim 1, wherein the composition furtherincludes:(d) at least one compound selected from the group consisting ofa compound of the general formula (V): ##STR13## wherein R¹⁶, R¹⁸ andR¹⁹ are the same or different and are hydrogen, an alkyl having 1 to 6carbon atoms, an alkoxy group having 1 to 6 carbon atoms, cyano,carboxylic acid, ester wherein the alkyl group has 1-4 carbon atoms,carboxylic acid alkyl amide wherein the alkyl group has 1 to 4 carbonatoms, nitro or halogen or R¹⁶ can form a condensed polycyclic grouptogether with the benzene ring, X is S, Se or N-R²⁰, R²⁰ is hydrogen, analkyl group having 1 to 6 carbon atoms, R¹⁷ is hydrogen, an alkyl having1 to 6 carbon atoms or phenyl or R¹⁷ --(CH═C)_(n) --X-- can form a 5membered ring condensed to the benzene ring, and n is 0 or 1, and acyclic diketone compound of the general formula ##STR14## wherein R²¹ ishydrogen, a substituted or unsubstituted alkyl group having 1 to 12carbon atoms or an aralkyl group having 7 to 20 carbon atoms, the arylmoiety of which has 6 to 10 oarbon atoms optionally substituted with analkyl of 1 to 4 carbon atoms and the alkyl moiety of which has 1 to 10carbon atoms and G is a bivalent organic group.
 4. A photopolymerizablecomposition according to claim 3, wherein the composition contains 0.01to 20 parts by weight of the component (d) per 100 parts by weight ofthe component (a).
 5. A photopolymerizable composition according toclaim 1, wherein the composition further includes 0 to 1000 parts byweight of a thermoplastic polymeric organic binder per 100 parts byweight of the component (a).